Zwitterionic polymer hairsetting compositions and method of using same

ABSTRACT

HAIRSETTING IS ACHIEVED WITH A SOLUTION CONTAINING A ZWITTERIONIC POLYMER HAVING CARBOXYLATE AND AMMONIUM FUNCTIONALITY.

United States Patent "Office 3,836,537 Patented Sept. 17, 1974 3,836,537ZWITTERIONIC POLYMER HAIRSE'I'IING COM- POSITIONS AND METHOD OF USINGSAME Fred P. Boerwinkle, Village of Lakeland, and Donald L. Waxberg,Village of Roseville, Minn. (both 3M Center, St. Paul, Minn. 55101) NoDrawing. Continuation-impart of abandoned application Ser. No. 78,968,Oct. 7, 1970. This application Oct. 25, 1972, Ser. No. 300,832

Int. Cl. C08f 29/46, 37/00, 37/18 U.S. 'Cl. 26029.6 HN 22 ClaimsABSTRACT OF THE DISCLOSURE Hairsetting is achieved with a solutioncontaining a zwitterionic polymer having carboxylate and ammoniumfunctionality.

CROSS-REFERENCE TO RELATED APPLICATION This is a continuation-in-part ofapplication Ser. No. 78,968, filed Oct. 7, 1970 and now abandoned.

BACKGROUND OF THE INVENTION Almost since the beginning of time womenhave employed compositions of some sort to make straight hair curly andto hold it in position after doing so. Perhaps the earliest materialemployed was plain water which was used to soften hair, but hair whichhas been moistened, curled, and dried in curled condition retains itsshape for only a short time. More recently, hair has been styled orarranged with solutions containing lacquers such as natural gums,resins, or synthetic plastics (e.g., polyvinyl pyrrolidone) which aredeposited on the fibers of the hair to hold them in place.

Such prior art lacquers are known for their characteristics of makinghair dulll, stiff, unnatural, sticky, and hard to clean. Many of themtend to flake unattractively. Some cause the hair to accumulate staticelectricity, making it difficult to comb or brush. Others, e.g.,polyvinyl pyrrolidone, absorb moisture from the air and become sticky ondamp days and hard and brittle in extremely dry weather. Still othersare adversely affected by water vapor, permitting treated hair to loseits curl in moist weather.

SUMMARY The present invention provides a hairsetting composition whichovercomes the objections inherent in the products of the prior art. Inthe practice of the invention, hair is imparted with a temporary settingwhich has excellent anti-static behavior and curl retention, gOOdcomb-out and sheen, and which is easily removed by shampooing.Additionally, the excellent curl-retention is maintained at highrelative humidity. The treated hair is flexible, readily arranged,pleasant smelling, clean, attractive, and glossy, retaining thesecharacteristics for several days, regardless of the relative humidity ofthe air.

It has been found that zwitterionic polymers, when applied to hairfibers, provide the above-described desirable properties, maintainingvery high curl-retention at high relative humidities.

In the context of the invention, the expressions zwitterionic polymerand zwitterionic monomer refer only to internally neutralized polymersand monomers con taining an acidic carboxylate group and a basicammonium group.

DETAILED DESCRIPTION OF THE INVENTION In accordance with the invention,hair is treated with an aqueous solution containing from about 0.25 toabout 10% by weight of zwitterionic polymer. Any one of a variety ofsuch polymers will be useful in the practice of the invention but twoparticular types which have been found to be especially useful will bedescribed below.

The aqueous solution of a zwitterionic polymer, to be useful fortreating hair, should be sufficiently viscous to remain on hair fiberswhen applied thereto, and sufficiently thin to effectively wet the hairfibers. It has been found that useful zwitterionic polymers have aviscosity of about to 100,000 cps., preferably about 1,000 to about25,000 cps., when tested at 24% solids in water with a Brookfieldviscometer, using the appropriate spindle and speed therefor.

Aqueous solutions of the zwitterionic polymer that have been found to bemost effective for setting hair have from about 0.25 to about 10% byweight, preferably about 1 to about 5%, of the zwitterionic polymer.Polymers having viscosities higher than those mentioned above whenmeasured as 24% solids aqueous solutions or hairsetting solutions havingexcess of 10% by Weight of zwitterionic polymer provide a stiffer curlwhich is more difficult to comb-out and cause the hair fibers to feelundesirably slippery during application.

The hairsetting solutions of the invention may contain an alcohol as aco-solvent with water, particularly when the zwitterionic polymer is acopolymer containing a water-insoluble monomer, as will be hereinafterdescribed. The solutions may also contain other additives that arenormally found in conventional hairsetting solutions such as perfumes,coloring dyes and the like.

It has been also discovered that the addition of a small amount ofzwitterionic polymer to prior art hairsetting solutions providesimproved curl-retention and anti-static behavior. The addition of aslittle as 0.25% by weight of zwitterionic polymer to such prior arthairsetting compositions has been found to be effective for suchpurposes.

PRESENTLY PREFERRED ZW'ITTERIONIC POLYMERS (A) Homopolymers andcopolymers may be prepared by polymerizing zwitterionic monomers havingthe general formula wherein R represents a polymerizable unsaturatedgroup, which permits homopolymerization of the monomer orcopolymerization with other polymerizable monomers. Such polymerizableunsaturated groups are preferably selected from the group consisting ofacrylate, methacrylate, acrylamide, and methacrylamide. Subscripts x andy represent an integer from 1 to 3 inclusive to provide methylene,ethylene, or propylene groups in the polymer backbone, groups largerthan 3 carbon atoms reducing the water solubility of the resultantpolymer such that it may not be useful as a hair-setting composition. Rand R represent hydrogen, methyl, ethyl or propyl radicals, larger alkylradicals reducing the water solubility of the polymer. R and R representa hydrogen atom or an alkyl radical, with the total sum of the carbonatoms in R and R not exceeding six, larger alkyl radicals also reducingthe water solubility of the polymer.

Typical zwitterionic monomers having the general formula shown above anduseful in preparing homopolymers or copolymers useful in the hairsettingcompositions of the invention, include, beta-methacryloxyethylbeta-dimethyl amino propionate betaine. Zwitterionic monomers of thistype may be prepared by methods known to the art, e.g., U.S. Pats.2,744,130, and 2,777,872.

The aforementioned zwitterionic monomers may either be homopolymerizedor copolymerized with other polymerizable monomers to provide thezwitterionic polymers useful for setting hair, the resultant polymerretaining the above-described desirable properties even when relativelylarge proportions of non-zwitterionic comonomer are used. Generally, thezwitterionic moiety of the desired copolymer should comprise at least,on a molar basis, about 10%, preferably at least about 20%, of thecopolymer to retain the above-described properties. Typicalwater-soluble non-zwitterionic monomers suitable for copolymerizationinclude vinyl pyrrolidone, dimethylaminoethyl acrylate,dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, anddiethylaminoethyl methacrylate.

Other non-zwitterionic monomers which are not watersoluble, such asalkyl acrylates or methacrylates, e.g., methyl acrylate, andacrylamides, methacrylamides, or vinyl acetate, may also becopolymerized with the previously mentioned zwitterionic monomers toprovide copolymers useful for setting hair. However, substantially lessof this type of non-zwitterionic monomer is utilized so as to maintainthe requisite solubility.

(B) Zwitterionic polymers containing carboxylate and ammoniumfunctionality are also prepared by copolymerizing a monomer having basicammonium functionality with monomer having acid carboxylatefunctionality. The acidic monomers are preferably substituted vinylcompounds of the general formula CR H=CR OO H, wherein R is a hydrogenatom or a CO H group and R is a hydrogen or chlorine atom or a methylgroup; exemplary compounds of this type include acrylic acid,methacrylic acid, maleic acid and a-chloroacrylic acid. The basicmonomers are preferably substituted vinyl compounds of the formula CH=CR COQ wherein R is a hydrogen atom or a methyl group and Q is anorganic radical containing a basic nitrogen-containing group, suchcompounds including dialkyl aminoalkyl methacrylates (e.g.,dimethylaminoethyl methacrylate), dialkyl aminoalkyl acrylates,N(1,1-dirnethyl-3-dimethyl-amino propyl) acrylamide methacrylaminopyridine, and the The zwitterionic copolymer produced from acidic andbasic monomers preferably will be formed of monomers of acrylic acid ormethacrylic acid polymerized with monomers of dimethylaminoethylmethacrylate or diethylaminoethyl acrylate.

For most purposes the mole ratio of basic monomer to the acidic monomerof the aforementioned zwitterionic copolymer ranges from 0.821 to 2.5:1, preferably 1:1 to 15:1. In the case of difunctional monomers,suitable adjustment should be made in mole ratios to maintain a similaracid-base balance. For monomers with difunc tional acidity, the ratio ofbasic monomer to acidic monomer will be 1.7 :1 to :1, preferably 2:1 to3:1. The resultant copolymer is preferably substantially completelyneutralized, although partially neutralized copolymers are also usefulfor setting hair.

The neutralizing agents are acidic and basic compounds which will not,once having served their function, produce substances which willdeleteriously affect hair or the copolymers ability to set hair. Acidicneutralizing agents include hydrochloric acid, acetic acid and the like.Basic neutralizing agents include ammonia, amines and the like.

Zwitterionic copolymers, besides being formed of acidic and basicmonomers, may include additional monomers which do not contain acidic orbasic groups, which may be added to reduce cost. Such monomers typicallyinclude lower alkyl acrylates or methacrylates, e.g., methyl acrylate,and acrylamides or methacrylamides. These neutral monomers, which can bewater-soluble or water-insoluble, will be contained in the copolymer inproportions which do not adversely affect the solubility of theresultant copolymer. Typically, water-insoluble monomers will be a minorproportion of the resultant copolymer.

The effectiveness of zwitterionic polymers for use in hairsettingcompositions is readily determined by means 4 of a curl retention testwhich also provides information with respect to anti-static behavior,comb-out, and sheen. In conducting the test, a predetermined weight ofhuman hair (approximately 6 inch length) is shampooed, rinsed withwater, saturated with the respective hairsetting composition beingtested, and combed four times. Each hair swatch is then wound on a hairroller, secured with bobby pins and dried at 140 F. for approximatelytwo and onehalf hours. Immediately following drying, the hair swatchesare unwound from the rollers, brushed five times, and are then ready fordetermination of curl retention.

Ten hair swatches are prepared for each hairsetting composition to betested. The initial hair length is recorded and the test swatches placedin a high relative humidity test environment (about relative humidity atabout 75 F. for one hour). The change in curl length is observedimmediately after the period of time in the humidity chamber, thepercent of curl retention being calculated by the formula t L X where Lis the length of the hair fully extended, L is the length of the hairwhen curled before exposure to the humidity environment, and L is thelength of the hair after exposure to the high humidity environment.Because factors such as humidity in the drying oven, etc. cause resultsto be somewhat different for tests conducted on different days, allcompositions are compared relative to a control sample evaluated at thesame time. The percent curl retention for each hairsetting compositionis then divided by the percent curl retention of the control andmultiplied by 100 to obtain the relative curl retention. The compositionof Example 1 was used as a control in each instance.

The following examples, in which all parts are by weight unlessotherwise indicated, illustrate preparation of the hairsettingcompositions of the invention, without limiting the scope thereof.

Example 1 As a control, polydimethylaminoethyl methacrylate fullyquaternized with methyl bromide was prepared and evaluated as ahairsetting lotion at 3% solids by weight in water, as disclosed inBritish Pat. 1,161,642. When tested by the previously described method,a relative curl retention of 100 was obtained.

Example 2 This example illustrates preparation of a hairsettingcomposition utilizing a zwitterionic polymer comprising an 80:20 moleratio copolymer of dimethylaminoethyl methacryloxyethyl, beta-dimethylaminopropionate betaine.

A polymerization flask fitted with a stirrer, nitrogen inlet,thermocouple, and addition funnel, was charged with 2842 gms. of water,315.2 gms. of a 37% hydrochloric acid water solution, 618 gms. ofdimethylaminoethyl methacrylate, and 225.2 gms. of beta-dimethyl,beta-methacryloxyethylamino propionate. betaine. The solution, withstirring, was evacuated to boiling for about 30 minutes, the flaskpurged with nitrogen, and the solution heated to 600 C. for 16 hours,during which time ml. of water containing 40 gms. of K S O was added infour equal portions about 30 minutes apart. The resultant polymersolution had a Brookfield viscosity of 16,600 cps. at 25 C. (#4 spindleat 30 r.p.rn.).

The polymer, at 3% solids in water, was evaluated as a hairsetting resinby the previously described test method, a relative curl retention of148, moderate comb-out, good sheen, and low static retention beingobtained.

Examples 3-12 The following polymers were prepared in a manner y areintegers from 1 to 3 inclusive, and R and R represent a hydrogen atom oran alkyl radical with the total sum of the carbon atoms in R and R notexceeding six, and

EXAMPLES 3l2 Composition Brookfield viscosity (cps.) and conditionsRelative Temp NaZSZOa, curl re- Example Monomers Mole ratio percent 24%Spindle R.p.m. 3% Spindle Rpm. tention o u 4 DMAEMA-betaine 1Homopolymer 60 0.5 9 21,500 4 154 DEAEA IMAA 3 50:50 60 1.0 .000 4 125 Xfi Dimethyl fi-methacryloxyethylaminopropionate betaine. 2Diethylaminoethyl acrylate.

3 Methacrylic acid.

4 Dimethylaminoethyl methacrylate.

5 Diethylaminoethyl methacrylate.

' N(l,1 dimethyl-3-dimethylaminopropyl) acrylamlde.

B 4% solids.

9 20% solids.

Example 14 Into a 5 liter flask was placed 2137 gms. anhydrous ethanol,160.5 g. acrylic acid mole percent), 350 gms. dimethylaminoethylmethacrylate (35 mole percent), 164.3 gms. methyl acrylate (30 molepercent) and 1.687 gms. azobisisobutyronitrile. The solution was heatedto 70 C. for 17 hrs, producing thereafter a white solution which wasdiluted with water to 3% solids to provide a hairsetting compositionwhich gave a relative curl retention of 136.

Example 15 A polymer was prepared in a manner similar to that describedin Example 14 except vinyl acetate was used in place of methyl acrylate.A relative curl retention of 119 was obtained with a 3 solution.

Example 16 A hairsetting composition was prepared containing 2.75percent by weight polyvinyl pyrrolidone and 0.25% by weight of thepolymer of Example 3 in water. Upon testing by the previously describedmethod, the composition was found to have a relative curly retention of106. As a comparison, a hairsetting lotion containing only 3% by weightpolyvinyl pyrrolidone, was tested in the previously described manner andwas found to have a relative curl retention of 86.

What is claimed is:

1. A method of setting hair comprising the sequential steps of (1)moistening the hair, (2) applying at ambient temperature an aqueoushairsetting composition comprising from about 0.25 to about 1 0% byweight of a zwitterionic polymer in water, said polymer containing atleast 10% on a molar basis of zwitterionic moiety, a 24% solids aqueoussolution of said polymer having a Brookfield viscosity of from about 100to 100,000 cps. (3) and drying the hair, thereby imparting to said hairexcellent anti-static behavior, comb-out, sheen, and high curl retentionmaintainable even at high relative humidity, said polymer being selectedfrom a group consisting of (A) polymers of carboxy betaines having therepeating wherein R represents a polymerizable unsaturated groupselected from the group consisting of acrylate, methacrylate, acrylamideand methacrylamide, R and R are hydrogen atoms or lower groups, x and10% solids.

11 Excess amine neutralized with HCl.

12 Excess amine neutralized with acetic acid. 13 Acrylamide.

14 Run at 12% solids.

1E 12% solids.

N-(y-methacryloxy, fl hydr0xypropyl)N-trimethyl ammonium chloride.

(B) copolymers of monomers (1) and (2), shown below:

(1) substituted acidic vinyl compounds having the general formula =CRH=CR CO H wherein R represents a hydrogen atom or a carboxylic acidgroup and R represents a hydrogen atom, a chlorine atom or a methylgroup, and

(2) substituted basic vinyl compounds having the general formula CH =CRCOQ wherein R represents a hydrogen atom or a methyl group and Q is anorganic radical containing a basic nitrogen-containing group, whereinsaid acidic and basic functionalities are retained in the copolymerstructure and wherein the mole ratio of basic monomer to acidic monomerin said copolymer is from 0.8:1 to 2.5:1, except where R; is CO H, themole ratio is 1.721 to 5:1.

2. The method of claim 1 wherein the (B)(l) monomers are selected fromthe group consisting of acrylic acid, maleic acid, u-chloroacrylic acidand methacrylic acid and the (B)(2) monomers are selected from the groupconsisting of dialkyl amino alkyl methacrylates, dialkylamino alkylacrylates and methacrylamino pyridine, wherein molar amounts of basicmonomer to acidic monomer in the copolymer are in a range of 0.8:1 to2.5 :1 with excess acid or excess base being substantially neutralized,except where R is CO H, the mole ratio is 1.7:1 to 5:1.

3. The method of claim 2 wherein said range of basic monomer to acidicmonomer in said copolymer is from 1:1 to 1.5 :1, except that where R isCO H, the mole ratio is 2:1 to 3:1.

4. The method of claim 1 wherein said zwitterionic polymer also containsnon-zwitterionic monomer.

5. The method of claim 4. wherein said non-zwitterionic monomer isselected from a group consisting of vinyl pyrrolidone, dialkylaminoalkylacrylates, dialkylaminoalkyl methacrylates, quaternary ammoniumacrylates, quaternary ammonium methacrylates, alkyl acrylates, alkylmethacrylates, acrylamides, methacrylamides, and vinyl acetate.

6. The method of claim 1 wherein said (B)(2) monomer is selected fromthe group consisting of N(1,1-dimethyl 3-dimethylaminopropyl)acrylamide, dimethylaminoethyl methacrylate, diethylaminoethylmethacrylate, and diethylaminoethyl acrylate and wherein said (B) (1)monomer is selected from the group acrylic acid and methacrylic acid.

7. The method of claim 1 wherein said (A) monomer isbeta-methacryloxyethyl beta-dimethyl aminopropionate betaine.

8. The method of claim 1 wherein R is selected from the group consistingof acrylate, methacrylate, acrylamide, and methacrylamide.

9. The method of claim 1 wherein x and y are 2.

10. The method of claim 1 wherein said aqueous hairsetting compositionalso contains an amount effective for setting hair of a water-solublehairsetting resin previously known for setting hair.

11. The method of claim 10 wherein said previously known resin ispolyvinyl pyrrolidone.

12. Method of claim 1 wherein said polymer is a copolymer ofdimethylaminoethyl methacrylate and betamethacryloxyethyl beta-dimethylaminopropionate betaine containing less than 30 mole percent ofdimethylaminoethyl methacrylate.

13. Method of claim 1 wherein said polymer is a copolymer of vinylacetate and beta-methacryloxyethyl betadimethyl aminopropionate betainecontaining less than 80 mole percent of vinyl acetate.

14. Method of claim 1 wherein the polymer is a copolymer ofbeta-dimethyl beta-methacryloxyethyl aminopropionate betaine and lessthan 30 mole percent of a comonomer selected from the group consistingof quaternary ammonium acrylates and quaternary ammonium methacrylates.

15. The method of claim 1 wherein said hairsetting composition containsfrom 1-5% by weight zwitterionic polymer.

16. A liquid composition for imparting to hair treated therewithstatic-free behavior, good comb-out andl sheen, and high curl retentionmaintainable even at high relative humidity, consisting essentially ofan aqueous solution containing from about 0.25 to about 10% by weight ofa zwitterionic polymer containing at least 10% on a molar basis ofzwitterionic moiety, a 24% solids aqueous solution of said polymerhaving a Brookfield viscosity of from about 100 to 100,000 cps, saidpolymer being a copolymer of monomers (1) and (2),

(1) substituted acidic vinyl compounds having the general formula CRH=CR OO H wherein R represents a hydrogen atom or a carboxylic acidgroup and R represents a hydrogen atom, a chlorine atom or a methylgroup, and

(2) substituted basic vinyl compounds having the general formula CH =CRCOQ wherein R represents a hydrogen atom or a methyl group and Q is anorganic radical containing a basic nitrogen-containing group whereinsaid acidic and basic functionalities are retained in the copolymerstructure, said acidic monomers being selected from the group consistingof acrylic acid, maleic acid, a-chloro-acrylic acid and methacrylic acidand said basic monomers being selected from the group consisting ofdiallrylamino alkyl methacrylates, dialkylamino alkyl acrylates andmethacrylamino pyridine, wherein the mole ratio of said basic monomer tosaid acidic monomer in said copolymer is from 0.8:1 to 2.5:1, exceptwhere R; is CO H when said mole ratio is 1.7:1 to :1.

17. The composition of claim 16 wherein said zwitterionic polymer alsocontains non-zwitterionic monomer.

18. The composition of claim 17 wherein said nonzwitterionic monomer isselected from a group consisting of vinyl pyrrolidone, dialkylaminoalkylacrylates, dialkylaminoalkyl methacrylates, quaternary ammoniumacrylates, quaternary ammonium methacrylates, alkyl acrylates, alkylmethacrylates, and vinyl acetate.

' 19. The composition of claim 16 wherein said basic monomer is selectedfrom the group consisting of N(l,ldimethyl-3-dimethylaminopropyl)acrylamide, dimethylaminoethyl methacrylate, and diethylaminoethylacrylate and wherein said acidic monomer is selected from the groupacrylic acid and methacrylic acid.

20. The composition of claim 16 wherein said hairsetting compositioncontains from 1-5% by weight zwitterionic polymer.

21. A liquid composition for imparting to hair treated therewithstatic-free behavior, good comb-out and sheen, and high curl retentionmaintainable even at high relative humidity, consisting essentially ofan aqueous solution cotaining from about 0.25 to about 10% by weight ofa zwitterionic polymer containing at least 10% on a molar basis ofzwitterionic moiety, a 24% solids aqueous solution of said polymerhaving a Brookfield viscosity of from about to 100,000 cps, said polymerbeing selected from a group consisting of (A) polymers of carboxybetaines having the repeating formula wherein R represents apolymerizable unsaturated group selected from the group consisting ofacrylate, methacrylate, acrylamide and methacrylamide, R and R arehydrogen atoms or lower alkyl groups, x and y are integers from 1 to 3inclusive, and R and R represent a hydrogen atom or an alkyl radicalwith the total sum of the carbon atoms in R and R not exceeding six, and

(B) copolymers of monomers (1) and (2), shown below:

(1) substituted acidic vinyl compounds having the general formula CRH=CR CO H wherein R represents a hydrogen atom or a carboxylic acidgroup and R represents a hydrogen atom, a chlorine atom or a methylgroup, and

(2) substituted basic vinyl compounds having the general formula OH =CRCOQ wherein R represents a hydrogen atom or a methyl group and Q is anorganic radical containing a basic nitrogen-containing group, whereinsaid acidic and basic functionalities are retained in the copolymerstructure and wherein the mole ratio of the basic monomer to acidicmonomer in said copolymer is from 0.8:1 to 2.5:1, except where R; is COH, the mole ratio is 1.7:1 to 5:1, wherein said aqueous hairsettingcomposition also contains an amount efiective for setting hair of awater-soluble hairsetting resin previously known for setting hair.

22. The composition of claim 21 wherein said previously known resin ispolyvinyl pyrrolidone.

References Cited UNITED STATES PATENTS 2,744,130 5/1956 Winberg 260-4822,777,872 1/1957 lShaoklett 260-482 2,833,650 5/1958 Shacklett 96-1142,834,758 5/1958 Shacklett 260-78 2,846,417 8/1958 Shacklett 260-783,598,641 8/1971 Miller et al 117-138.8 E 3,671,305 6/1972 Brown et al.117-1388 F 3,689,470 9/1972 Shachat et al. 260-861 N OTHER REFERENCESMitra et al. J. Electroanal. Chem. 15, 399-404 (1967).

Ryabov et al., Tr. Khim. Khim. T eckhnoL, 1967(2), 49-51.

Ryabov et al., Tr. Kkim. Khim. TecknoL, 1968(1), 51-55.

MELVIN GOLDSTEIN, Primary Examiner US. Cl. X.R.

132-7; 260-2936 WB; 424-71, Dig. 2

